US20240021871A1 - Solid electrolyte material and battery using same - Google Patents

Solid electrolyte material and battery using same Download PDF

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US20240021871A1
US20240021871A1 US18/469,587 US202318469587A US2024021871A1 US 20240021871 A1 US20240021871 A1 US 20240021871A1 US 202318469587 A US202318469587 A US 202318469587A US 2024021871 A1 US2024021871 A1 US 2024021871A1
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solid electrolyte
electrolyte material
material according
battery
positive electrode
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Takuya Naruse
Tomoyasu Yokoyama
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Panasonic Intellectual Property Management Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a solid electrolyte material and a battery using the same.
  • WO 2020/137043 discloses a lithium ion-conductive solid electrolyte material constituted of Li, La, O, and X and an all-solid-state battery using the material.
  • X is at least one element selected from the group consisting of Cl, Br, and I.
  • One non-limiting and exemplary embodiment provides a solid electrolyte material suitable for improving lithium ion conductivity.
  • the techniques disclosed here feature a solid electrolyte material including Li, La, O, X, and a hydride, wherein the X is at least one selected from the group consisting of F, Cl, Br, and I.
  • the present disclosure provides a solid electrolyte material suitable for improving lithium ion conductivity.
  • FIG. 1 shows a cross-sectional view of a battery 1000 according to a second embodiment
  • FIG. 2 is a cross-sectional view of an electrode material 1100 according to the second embodiment
  • FIG. 3 shows a schematic diagram of a compression molding dies 300 used for evaluation of the ion conductivity of a solid electrolyte material
  • FIG. 4 is a graph showing a cole-cole plot obtained by impedance measurement of a solid electrolyte material of Example 1;
  • FIG. 5 is a graph showing the initial charge and discharge characteristics of a battery of Example 1.
  • FIG. 6 is a graph showing X-ray diffraction patterns of solid electrolyte materials of Examples 1 to 5 and Comparative Example 1.
  • the solid electrolyte material according to a first embodiment includes Li, La, O, X, and a hydride.
  • X is at least one selected from the group consisting of F, Cl, Br, and I.
  • the solid electrolyte material according to the first embodiment is a solid electrolyte material suitable for improving lithium ion conductivity.
  • the solid electrolyte material according to the first embodiment can have, for example, practical lithium ion conductivity and can have, for example, high lithium ion conductivity.
  • high lithium ion conductivity is, for example, greater than or equal to 3 ⁇ 10 ⁇ 5 S/cm at around room temperature (e.g., 25° C.). That is, the solid electrolyte material according to the first embodiment can have, for example, an ion conductivity of greater than or equal to 3 ⁇ 10 ⁇ 5 S/cm.
  • the solid electrolyte material according to the first embodiment can be used for obtaining a battery with excellent charge and discharge characteristics.
  • An example of the battery is an all-solid-state battery.
  • the all-solid-state battery may be a primary battery or a secondary battery.
  • the solid electrolyte material according to the first embodiment does not substantially contain sulfur.
  • the fact that the solid electrolyte material according to the first embodiment does not substantially contain sulfur means that the solid electrolyte material does not contain sulfur as a constitutional element, except for sulfur inevitably mixed as an impurity. In this case, the amount of sulfur as an impurity mixed in the solid electrolyte material is, for example, less than or equal to 1 mol %.
  • the solid electrolyte material according to the first embodiment does not contain sulfur.
  • a solid electrolyte material not containing sulfur does not generate hydrogen sulfide, even if it is exposed to the atmosphere, and is therefore excellent in safety.
  • the sulfide solid electrolyte disclosed in International Publication No. WO 2020/137043 may generate hydrogen sulfide when exposed to the atmosphere.
  • the solid electrolyte material according to the first embodiment may consist essentially of Li, La, O, X, and a hydride.
  • the fact that “the solid electrolyte material according to the first embodiment consists essentially of Li, La, O, X, and a hydride” means that the proportion of the total amount of Li, La, O, X, and a hydride to the total amount of all elements constituting the solid electrolyte material according to the first embodiment is greater than or equal to 90%.
  • the molar proportion may be greater than or equal to 95%.
  • the solid electrolyte material according to the first embodiment may consist of Li, La, O, X, and a hydride only.
  • the solid electrolyte material according to the first embodiment may contain inevitably mixed elements.
  • An example of the element is nitrogen.
  • Such an element may be present in the raw material powders of the solid electrolyte material or in the atmosphere for manufacturing or storing the solid electrolyte material.
  • the amount of the elements inevitably mixed in the solid electrolyte material according to the first embodiment as described above is, for example, less than or equal to 1 mol %.
  • the solid electrolyte material according to the first embodiment further includes a hydride in addition to Li, La, O, and X.
  • a hydride in addition to Li, La, O, and X.
  • the hydride is an ionic hydride including an anion
  • the interaction of the anion with Li + is weak compared to that of a halide ion such as I ⁇ . Accordingly, it is inferred that since the hydride is unlikely to restrict Li + and thereby Li + easily conducts, the solid electrolyte material according to the first embodiment can improve the lithium ion conductivity.
  • the ratio of the amount of O to the total amount of X and the hydride may be less than 1.
  • Such a solid electrolyte material has improved lithium ion conductivity.
  • the ratio of the amount of 0 to the total amount of I and the borohydride compound including BH 4 ⁇ may be less than 1.
  • the ratio of the amount of Li to the amount of La may be greater than or equal to 0.75 and less than or equal to 2.0.
  • the ratio of the amount of the hydride to the amount of X may be greater than 0 and less than or equal to 2.0.
  • the ratio of the amount of the hydride including BH 4 ⁇ to the amount of I may be greater than 0 and less than or equal to 2.0.
  • the hydride may include, for example, a boron atom.
  • a solid electrolyte material has improved lithium ion conductivity.
  • the hydride including a boron atom may include, for example, at least one selected from the group consisting of a borohydride compound including BH 4 ⁇ and a carborane.
  • a borohydride compound including BH 4 ⁇ and a carborane An example of the carborane is C 2 B 10 H 12 .
  • Such a solid electrolyte material has more improved lithium ion conductivity.
  • the hydride may include a borohydride compound including BH 4 ⁇ .
  • the hydride may be a borohydride compound including BH 4 ⁇ .
  • the hydride need not include boron.
  • the hydride may include, for example, a nitrogen atom.
  • the hydride including a nitrogen atom are an amidide or an imidide.
  • the amidide may be, for example, LiNH 2 .
  • the imidide may be, for example, Li 2 NH.
  • X may include I.
  • X may be I.
  • the solid electrolyte material according to the first embodiment may be a composite material including LaOX and a hydride. Such a solid electrolyte material has more improved ion conductivity.
  • the solid electrolyte material according to the first embodiment may be a material represented by the following formula (1). That is, the solid electrolyte material according to the first embodiment may be a composite material including LaOX and lithium borohydride (LiBH 4 ) as the hydride.
  • LiBH 4 lithium borohydride
  • the solid electrolyte material represented by the formula (1) has improved lithium ion conductivity.
  • Li + constituting LiX is attracted to LaOX, and the Li + conducts, that is, Li + conducts in the interface between LiX and LaOX.
  • LiBH 4 is also included as a hydride. LiBH 4 interacts with Li + weaker than X. That is, Li + constituting LiBH 4 is more easily attracted to the LaOX side. Consequently, it is inferred that the solid electrolyte material represented by the formula (1) including LiBH 4 can improve the lithium ion conductivity.
  • a ⁇ b may be satisfied.
  • the upper limit and lower limit of the range of “a” in the formula (1) may be prescribed by an arbitrary combination of numerical values selected from the group consisting of 0, 0.4, 0.8, 1.2, 1.6, and 2.0.
  • the upper limit and lower limit of the range of “b” in the formula (1) may be prescribed by an arbitrary combination of numerical values selected from the group consisting of 0.4, 0.8, 1.0, 1.2, 1.6, and 2.0.
  • X may be I.
  • the solid electrolyte material according to the first embodiment may be crystalline or amorphous.
  • the shape of the solid electrolyte material according to the first embodiment is not limited. Examples of the shape are needle, spherical, and oval spherical shapes.
  • the solid electrolyte material according to the first embodiment may be a particle.
  • the solid electrolyte material according to the first embodiment may have a pellet or planar shape.
  • the solid electrolyte material according to the first embodiment is a particulate shape (e.g., spherical)
  • the solid electrolyte material may have a median diameter of greater than or equal to 0.1 ⁇ m and less than or equal to 100 ⁇ m or a median diameter of greater than or equal to 0.5 ⁇ m and less than or equal to 10 ⁇ m. Consequently, the solid electrolyte material according to the first embodiment and another material can be well dispersed.
  • the median diameter of particles means the particle diameter (d50) at the accumulated volume of 50% in a volume-based particle size distribution.
  • the volume-based particle size distribution can be measured with a laser diffraction measurement apparatus or an image analyzer.
  • the solid electrolyte material according to the first embodiment can be manufactured by the following method.
  • Raw material powders are provided so as to give a target composition.
  • composition ratio of a target solid electrolyte material is 1.0LaOI ⁇ 1.6LiI ⁇ 0.4LiBH 4
  • a Li 2 O raw material powder, a LiBH 4 raw material powder, a La 2 O 3 raw material powder, and a LaI 3 raw material powder are mixed at a molar ratio of 12:6:1:13.
  • the raw material powders may be mixed at a molar ratio adjusted in advance such that a composition change which may occur during the synthesis process is offset.
  • raw material powders are mechanochemically reacted (i.e., using a mechanochemical method) with each other in a mixing apparatus such as a planetary ball mill to obtain a reaction product.
  • a mixing apparatus such as a planetary ball mill
  • the solid electrolyte material according to the first embodiment is obtained by such a method.
  • the composition of the solid electrolyte material can be determined by, for example, ICP emission spectrometry, ion chromatography, an inert gas fusion-infrared absorbing method, or an electron probe micro analyzer (EPMA) method.
  • ICP emission spectrometry ion chromatography
  • I inert gas fusion-infrared absorbing method
  • EPMA electron probe micro analyzer
  • the compositions of Li and La are determined by ICP emission spectrometry
  • the composition of I is determined by ion chromatography
  • O can be measured by an inert gas fusion-infrared absorbing method.
  • the hydride can be analyzed and the quantitative ratio can be evaluated by, for example, EPMA or X-ray photoelectron spectroscopy (XPS).
  • the battery according to the second embodiment includes a positive electrode, a negative electrode, and an electrolyte layer.
  • the electrolyte layer is disposed between the positive electrode and the negative electrode.
  • At least one selected from the group consisting of the positive electrode, the electrolyte layer, and the negative electrode contains the solid electrolyte material according to the first embodiment.
  • the battery according to the second embodiment contains the solid electrolyte material according to the first embodiment and therefore has excellent charge and discharge characteristics.
  • the battery may be an all-solid-state battery.
  • FIG. 1 shows a cross-sectional view of a battery 1000 according to the second embodiment.
  • the battery 1000 according to the second embodiment includes a positive electrode 201 , an electrolyte layer 202 , and a negative electrode 203 .
  • the electrolyte layer 202 is disposed between the positive electrode 201 and the negative electrode 203 .
  • the positive electrode 201 contains a positive electrode active material particle 204 and a solid electrolyte particle 100 .
  • the electrolyte layer 202 contains an electrolyte material.
  • the electrolyte material is, for example, a solid electrolyte material.
  • the negative electrode 203 contains a negative electrode active material particle 205 and a solid electrolyte particle 100 .
  • the solid electrolyte particle 100 includes the solid electrolyte material according to the first embodiment.
  • the solid electrolyte particle 100 may be a particle including the solid electrolyte material according to the first embodiment as a main component.
  • the particle including the solid electrolyte material according to the first embodiment as a main component means a particle in which the component with the highest molar ratio is the solid electrolyte material according to the first embodiment.
  • the solid electrolyte particle 100 may be a particle consisting of the solid electrolyte material according to the first embodiment.
  • the solid electrolyte particle 100 may have a median diameter of greater than or equal to 0.1 ⁇ m and less than or equal to 100 ⁇ m or a median diameter of greater than or equal to 0.5 ⁇ m and less than or equal to 10 ⁇ m. In such a case, the solid electrolyte particle 100 has higher ion conductivity.
  • the positive electrode 201 contains a material that can occlude and release metal ions such as lithium ions.
  • the positive electrode 201 contains, for example, a positive electrode active material (for example, the positive electrode active material particle 204 ).
  • Examples of the positive electrode active material are a lithium-containing transition metal oxide, a transition metal fluoride, a polyanionic material, a fluorinated polyanionic material, a transition metal sulfide, a transition metal oxyfluoride, a transition metal oxysulfide, and a transition metal oxynitride.
  • Examples of the lithium-containing transition metal oxide are LiN 1-d-f Co d Al f O 2 (here, 0 ⁇ d, 0 ⁇ f, and 0 ⁇ (d+f) ⁇ 1) and LiCoO 2 .
  • lithium phosphate may be used as a positive electrode active material.
  • the positive electrode 201 may contain a transition metal oxyfluoride as a positive electrode active material, in addition to the solid electrolyte material according to the first embodiment.
  • the solid electrolyte material according to the first embodiment even if it is fluorinated by the transition metal oxyfluoride, hardly forms a resistive layer. As a result, the battery 1000 has high charge and discharge efficiency.
  • the transition metal oxyfluoride contains oxygen and fluorine.
  • the transition metal oxyfluoride may be a compound represented by Li p Me′ q O m F n , where Me′ is at least one selected from the group consisting of Mn, Co, Ni, Fe, Al, Cu, V, Nb, Mo, Ti, Cr, Zr, Zn, Na, K, Ca, Mg, Pt, Au, Ag, Ru, W, B, Si, and P, and mathematical expressions: 0.5 ⁇ p ⁇ 1.5, 0.5 ⁇ q ⁇ 1.0, 1 ⁇ m ⁇ 2, and 0 ⁇ n ⁇ 1 are satisfied.
  • An example of such a transition metal oxyfluoride is Li 1.05 (Ni 0.35 Co 0.35 Mn 0.3 ) 0.95 O 1.9 F 0.1 .
  • the positive electrode active material particle 204 may have a median diameter of greater than or equal to 0.1 ⁇ m and less than or equal to 100 ⁇ m.
  • the positive electrode active material particle 204 has a median diameter of greater than or equal to 0.1 ⁇ m, the positive electrode active material particle 204 and the solid electrolyte particle 100 can be well dispersed in the positive electrode 201 . Consequently, the charge and discharge characteristics of the battery are improved.
  • the positive electrode active material particle 204 has a median diameter of less than or equal to 100 ⁇ m, the lithium diffusion speed in the positive electrode active material particle 204 is improved. Consequently, the battery can operate at high output.
  • the positive electrode active material particle 204 may have a median diameter larger than that of the solid electrolyte particle 100 . Consequently, the positive electrode active material particle 204 and the solid electrolyte particle 100 can be well dispersed.
  • the ratio of the volume of the positive electrode active material particle 204 to the sum of the volume of the positive electrode active material particle 204 and the volume of the solid electrolyte particle 100 may be greater than or equal to 0.30 and less than or equal to 0.95.
  • FIG. 2 shows a cross-sectional view of an electrode material 1100 according to the second embodiment.
  • the electrode material 1100 is included in, for example, the positive electrode 201 .
  • a covering layer 216 may be formed on the surface of the electrode active material particle 206 . Consequently, it is possible to suppress the increase in the reaction overpotential of the battery.
  • the covering material included in the covering layer 216 are a sulfide solid electrolyte, an oxide solid electrolyte, and a halide solid electrolyte.
  • the covering material may be lithium niobate which has excellent stability even at high potential.
  • the positive electrode 201 may be composed of a first positive electrode layer containing a first positive electrode active material and a second positive electrode layer containing a second positive electrode active material.
  • the second positive electrode layer is disposed between the first positive electrode layer and the electrolyte layer 202 .
  • the first positive electrode layer and the second positive electrode layer contain the solid electrolyte material according to the first embodiment, and a covering layer may be formed on the surface of the second positive electrode active material. According to the configuration above, it is possible to suppress the oxidation of the solid electrolyte material according to the first embodiment included in the electrolyte layer 202 due to the second positive electrode active material. As a result, the battery has a high charging capacity.
  • Examples of the covering material included in the covering layer 216 are a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, and a halide solid electrolyte.
  • the first positive electrode active material may be the same material as the second positive electrode active material or may be a different material from the second positive electrode active material.
  • the positive electrode 201 may have a thickness of greater than or equal to 10 ⁇ m and less than or equal to 500 ⁇ m.
  • the electrolyte layer 202 contains an electrolyte material.
  • the electrolyte material is, for example, a solid electrolyte material.
  • the electrolyte layer 202 may be a solid electrolyte layer.
  • the electrolyte layer 202 may contain the solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may consist of the solid electrolyte material according to the first embodiment only.
  • the solid electrolyte material according to the first embodiment is referred to as a first solid electrolyte material
  • the solid electrolyte material that is different from the solid electrolyte material according to the first embodiment is referred to as a second solid electrolyte material.
  • the electrolyte layer 202 may contain the second solid electrolyte material.
  • the electrolyte layer 202 may consist of the second solid electrolyte material only.
  • the electrolyte layer 202 may contain not only the first solid electrolyte material but also the second solid electrolyte material.
  • the first solid electrolyte material and the second solid electrolyte material may be uniformly dispersed in the electrolyte layer 202 .
  • the electrolyte layer 202 may have a thickness of greater than or equal to 1 ⁇ m and less than or equal to 100 ⁇ m. When the electrolyte layer 202 has a thickness of greater than or equal to 1 ⁇ m, the positive electrode 201 and the negative electrode 203 are less likely to be short-circuited. When the electrolyte layer 202 has a thickness of less than or equal to 100 ⁇ m, the battery can operate at high output.
  • Another electrolyte layer may be further provided between the electrolyte layer 202 and the negative electrode 203 .
  • the second electrolyte layer may be constituted of another solid electrolyte material that is electrochemically more stable than the first solid electrolyte material.
  • the reduction potential of the solid electrolyte material constituting the second electrolyte layer may be lower than that of the first solid electrolyte material. Consequently, the first solid electrolyte material can be used without being reduced. As a result, the charge and discharge efficiency of the battery can be improved.
  • the negative electrode 203 contains a material that can occlude and release metal ions such as lithium ions.
  • the negative electrode 203 contains, for example, a negative electrode active material (for example, the negative electrode active material particle 205 ).
  • Examples of the negative electrode active material are a metal material, a carbon material, an oxide, a nitride, a tin compound, and a silicon compound.
  • the metal material may be a single metal or an alloy.
  • Examples of the metal material are a lithium metal and a lithium alloy.
  • Examples of the carbon material are natural graphite, coke, graphitizing carbon, carbon fibers, spherical carbon, artificial graphite, and amorphous carbon. From the viewpoint of the capacity density, suitable examples of the negative electrode active material are silicon (i.e., Si), tin (i.e., Sn), a silicon compound, and a tin compound.
  • the negative electrode active material may be selected based on the reduction resistance of the solid electrolyte material included in the negative electrode 203 .
  • a material that can occlude and release lithium ions at greater than or equal to 0 V against lithium may be used as the negative electrode active material.
  • the negative electrode active material is such a material, it is possible to suppress the reduction of the first solid electrolyte material included in the negative electrode 203 .
  • the battery has high charge and discharge efficiency.
  • the material are titanium oxide, an indium metal, and a lithium alloy.
  • Examples of the titanium oxide are Li 4 Ti 5 O 12 , LiTi 2 O 4 , and TiO 2 .
  • the negative electrode active material particle 205 may have a median diameter of greater than or equal to 0.1 ⁇ m and less than or equal to 100 ⁇ m.
  • the negative electrode active material particle 205 has a median diameter of greater than or equal to 0.1 ⁇ m, the negative electrode active material particle 205 and the solid electrolyte particle 100 can be well dispersed in the negative electrode 203 . Consequently, the charge and discharge characteristics of the battery are improved.
  • the negative electrode active material particle 205 has a median diameter of less than or equal to 100 ⁇ m, the lithium diffusion speed in the negative electrode active material particle 205 is improved. Consequently, the battery can operate at high output.
  • the negative electrode active material particle 205 may have a median diameter larger than that of the solid electrolyte particle 100 . Consequently, the negative electrode active material particle 205 and the solid electrolyte particle 100 can be well dispersed.
  • the ratio of the volume of the negative electrode active material particle 205 to the sum of the volume of the negative electrode active material particle 205 and the volume of the solid electrolyte particle 100 may be greater than or equal to 0.30 and less than or equal to 0.95.
  • the electrode material 1100 shown in FIG. 2 may be included in the negative electrode 203 .
  • a covering layer 216 may be formed on the surface of the electrode active material particle 206 . Consequently, the battery has high charge and discharge efficiency.
  • the covering material included in the covering layer 216 are a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, and a halide solid electrolyte.
  • the covering material may be a sulfide solid electrolyte or a polymer solid electrolyte.
  • a sulfide solid electrolyte is Li 2 S—P 2 S 5 .
  • the polymer solid electrolyte are polyethylene oxide and a conjugated compound of a lithium salt.
  • An example of such a polymer solid electrolyte is lithium bis(trifluoromethanesulfonyl)imide.
  • the negative electrode 203 may have a thickness of greater than or equal to 10 ⁇ m and less than or equal to 500 ⁇ m.
  • At least one selected from the group consisting of the positive electrode 201 , the electrolyte layer 202 , and the negative electrode 203 may contain a second solid electrolyte material for the purpose of enhancing the ion conductivity, chemical stability, and electrochemical stability.
  • the second solid electrolyte material are a sulfide solid electrolyte, an oxide solid electrolyte, a halide solid electrolyte, and an organic polymer solid electrolyte.
  • the “sulfide solid electrolyte” means a solid electrolyte containing sulfur.
  • the “oxide solid electrolyte” means a solid electrolyte containing oxygen.
  • the oxide solid electrolyte may contain an anion (provided that sulfur and halogen elements are excluded) other than oxygen.
  • the “halide solid electrolyte” means a solid electrolyte containing a halogen element and not containing sulfur.
  • the halide solid electrolyte may contain not only a halogen element but also oxygen.
  • Examples of the sulfide solid electrolyte are Li 2 S—P 2 S 5 , Li 2 S—SiS 2 , Li 2 S—B 2 S 3 , Li 2 S—GeS 2 , Li 3.25 Ge 0.25 P 0.75 S 4 , and Li 10 GeP 2 S 12 .
  • oxide solid electrolyte examples are:
  • halide solid electrolyte material examples are compounds represented by Li a Me b Y c Z 6 .
  • Me is at least one element selected from the group consisting of metal elements and metalloid elements excluding Li and Y;
  • Z is at least one selected from the group consisting of F, Cl, Br, and I; and the value of m represents the valence of Me.
  • the “metalloid elements” are B, Si, Ge, As, Sb, and Te.
  • the “metal elements” are all elements (excluding hydrogen) included in Groups 1 to 12 of the periodic table and all elements (excluding B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se) included in Groups 13 to 16 of the periodic table.
  • Me may be at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb.
  • the halide solid electrolyte for example, Li 3 YCl 6 or Li 3 YBr 6 is used.
  • the negative electrode 203 may contain a sulfide solid electrolyte. Consequently, the sulfide solid electrolyte which is electrochemically stable against the negative electrode active material can suppress the contact between the first solid electrolyte material and the negative electrode active material. As a result, the internal resistance of the battery is reduced.
  • Examples of the organic polymer solid electrolyte are a polymer compound and a compound of a lithium salt.
  • the polymer compound may have an ethylene oxide structure.
  • a polymer compound having an ethylene oxide structure can contain a large amount of a lithium salt and therefore can further enhance the ion conductivity.
  • lithium salt examples include LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiSO 3 CF 3 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 CF 3 )(SO 2 C 4 F 9 ), and LiC(SO 2 CF 3 ) 3 .
  • One lithium salt selected from these salts may be used alone. Alternatively, a mixture of two or more lithium salts selected from these salts may be used.
  • At least one selected from the group consisting of the positive electrode 201 , the electrolyte layer 202 , and the negative electrode 203 may contain a nonaqueous electrolytic liquid, a gel electrolyte, or an ionic liquid for the purpose of facilitating the transfer of lithium ions and improving the output characteristics of the battery.
  • the nonaqueous electrolytic liquid contains a nonaqueous solvent and a lithium salt dissolved in the nonaqueous solvent.
  • nonaqueous solvent examples include a cyclic carbonate solvent, a chain carbonate solvent, a cyclic ether solvent, a chain ether solvent, a cyclic ester solvent, a chain ester solvent, and a fluorine solvent.
  • examples of the cyclic carbonate solvent are ethylene carbonate, propylene carbonate, and butylene carbonate.
  • Examples of the chain carbonate solvent are dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate.
  • Examples of the cyclic ether solvent are tetrahydrofuran, 1,4-dioxane, and 1,3-dioxolane.
  • Examples of the chain ether solvent are 1,2-dimethoxyethane and 1,2-diethoxyethane.
  • cyclic ester solvent is y-butyrolactone.
  • chain ester solvent is methyl acetate.
  • fluorine solvent are fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, fluoroethyl methyl carbonate, and fluorodimethylene carbonate.
  • One nonaqueous solvent selected from these solvents may be used alone. Alternatively, a mixture of two or more nonaqueous solvents selected from these solvents may be used.
  • lithium salt examples include LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiSO 3 CF 3 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 CF 3 )(SO 2 C 4 F 9 ), and LiC(SO 2 CF 3 ) 3 .
  • One lithium salt selected from these salts may be used alone. Alternatively, a mixture of two or more lithium salts selected from these salts may be used.
  • the concentration of the lithium salt may be, for example, greater than or equal to 0.5 mol/L and less than or equal to 2 mol/L.
  • a polymer material impregnated with a nonaqueous electrolytic liquid can be used as the gel electrolyte.
  • the polymer material are polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, and a polymer having an ethylene oxide bond.
  • Examples of the cation included in the ionic liquid are:
  • Examples of the anion included in the ionic liquid are PF 6 ⁇ , BF 4 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , SO 3 CF 3 ⁇ , N(SO 2 CF 3 ) 2 ⁇ , N(SO 2 C 2 F 5 ) 2 ⁇ , N(SO 2 CF 3 )(SO 2 C 4 F 9 ) ⁇ , and C(SO 2 CF 3 ) 3 ⁇ .
  • the ionic liquid may contain a lithium salt.
  • At least one selected from the group consisting of the positive electrode 201 , the electrolyte layer 202 , and the negative electrode 203 may contain a binder for the purpose of improving the adhesion between individual particles.
  • binder examples include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, polyacrylic acid hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyether sulfone, hexafluoropolypropylene, styrene butadiene rubber, and carboxymethyl cellulose.
  • a copolymer can also be used as the binder.
  • a binder are copolymers of two or more materials selected from the group consisting of tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene.
  • a mixture of two or more selected from the above-mentioned materials may be used as the binder.
  • At least one selected from the positive electrode 201 and the negative electrode 203 may contain a conductive assistant for the purpose of enhancing the electron conductivity.
  • Examples of the conductive assistant are:
  • the conductive assistant of the above (i) or (ii) may be used.
  • Examples of the shape of the battery according to the second embodiment are coin type, cylindrical type, square type, sheet type, button type, flat type, and laminated type.
  • the battery according to the second embodiment may be manufactured by, for example, providing a material for forming the positive electrode, a material for forming the electrolyte layer, and a material for forming the negative electrode and producing a layered product in which the positive electrode, the electrolyte layer, and the negative electrode are disposed in this order by a known method.
  • Li 2 O, LiBH 4 , La 2 O 3 , and LaI 3 were provided as raw material powders at a molar ratio of 12:6:1:13 in an argon atmosphere having a dew point of less than or equal to ⁇ 60° C. (hereinafter, referred to as “dry argon atmosphere”).
  • dry argon atmosphere argon atmosphere having a dew point of less than or equal to ⁇ 60° C.
  • the mixture of these raw material powders was milled with a planetary ball mill at 500 rpm for 30 hours.
  • the solid electrolyte material powder of Example 1 was obtained.
  • the solid electrolyte material of Example 1 had a composition represented by 1.0LaOI ⁇ 1.6LiI ⁇ 0.4LiBH 4 .
  • the composition here is a charge composition calculated from the charge amount.
  • the composition of the obtained solid electrolyte material was almost the same as the charge composition in the manufacturing method used in the present example.
  • the solid electrolyte material was produced by milling treatment with a ball mill, and diffraction peaks showing the presence of LaOI, LiI, and LiBH 4 were observed in an X-ray diffraction pattern obtained by X-ray diffraction measurement of the obtained solid electrolyte material. Accordingly, it is inferred that the obtained solid electrolyte material of Example 1 is a composition material including LaOI, LiI, and LiBH 4 .
  • FIG. 6 is a graph showing an X-ray diffraction pattern of the solid electrolyte material of Example 1.
  • FIG. 3 shows a schematic diagram of a compression molding dies 300 used for evaluation of the ion conductivity of a solid electrolyte material.
  • the compression molding dies 300 included a punch upper part 301 , a die 302 , and a punch lower part 303 .
  • the die 302 was formed from insulating polycarbonate.
  • the punch upper part 301 and the punch lower part 303 were both formed from electron-conductive stainless steel.
  • the ion conductivity of the solid electrolyte material of Example 1 was measured using the compression molding dies 300 shown in FIG. 3 by the following method.
  • the powder of the solid electrolyte material of Example 1 (i.e., the powder 101 of the solid electrolyte material in FIG. 3 ) was loaded inside the compression molding dies 300 in a dry atmosphere having a dew point of less than or equal to ⁇ 30° C.
  • a pressure of 400 MPa was applied to the solid electrolyte material of Example 1 inside the compression molding dies 300 using the punch upper part 301 .
  • the punch upper part 301 and the punch lower part 303 were connected to a potentiostat (Bio-Logic Science Instruments Ltd, VMP-300) equipped with a frequency response analyzer, while applying the pressure.
  • the punch upper part 301 was connected to the working electrode and the potential measurement terminal.
  • the punch lower part 303 was connected to the counter electrode and the reference electrode.
  • the ion conductivity of the solid electrolyte material of Example 1 was measured by an electrochemical impedance measurement method at room temperature.
  • FIG. 4 is a graph showing a cole-cole plot obtained by impedance measurement of the solid electrolyte material of Example 1.
  • the real value of impedance at the measurement point where the absolute value of the phase of the complex impedance was the smallest was regarded as the resistance value of the solid electrolyte material against ion conduction.
  • the real value see the arrow R SE shown in FIG. 4 .
  • the ion conductivity was calculated using the resistance value based on the following mathematical expression (2):
  • ⁇ represents ion conductivity
  • S represents the contact area of a solid electrolyte material with the punch upper part 301 (equal to the cross-sectional area of the hollow part of the die 302 in FIG. 3 );
  • R SE represents the resistance value of the solid electrolyte material in impedance measurement;
  • t represents the thickness of the solid electrolyte material (i.e., equal to the thickness of the layer formed from the powder 101 of the solid electrolyte material in FIG. 3 ) applied with a pressure.
  • the ion conductivity of the solid electrolyte material of Example 1 measured at room temperature was 1.03 ⁇ 10 ⁇ 4 S/cm.
  • the solid electrolyte material of Example 1, Li 4 Ti 5 O 12 , and a carbon fiber (VGCF) were provided at a mass ratio of 30:65:5 in a dry argon atmosphere. These materials were mixed in a mortar. Thus, a mixture was obtained.
  • VGCF is a registered trademark of Resonac Corporation.
  • metal In foil, metal Li foil, and metal In foil were stacked in this order on the solid electrolyte layer.
  • a pressure of 40 MPa was applied to this layered product to form a counter electrode.
  • a current collector formed from stainless steel was attached to the electrode and the counter electrode, and a current collecting lead was attached to the current collector.
  • FIG. 5 is a graph showing the initial discharge and discharge characteristics of the battery of Example 1. The initial charge and discharge characteristics were measured by the following method.
  • Example 1 The battery of Example 1 was disposed in a thermostat of 25° C.
  • Example 1 The battery of Example 1 was charged at a current density of 17.1 ⁇ A/cm 2 until the voltage reached 0.58 V.
  • the current density corresponds to 0.01 C rate.
  • Example 1 the battery of Example 1 was discharged at a current density of 17.1 ⁇ A/cm 2 until the voltage reached 1.0 V.
  • the current density corresponds to 0.01 C rate.
  • the battery of Example 1 had an initial discharge capacity of 829 ⁇ Ah.
  • Li 2 O, LiBH 4 , LaI 3 , and La 2 O 3 were provided at a molar ratio of (a/2):b:((1+a)/3):((2 ⁇ a)/6)).
  • the values of “a” and “b” are shown in Table 1.
  • FIG. 6 is a graph showing X-ray diffraction patterns of the solid electrolyte materials of Examples 2 to 5 and Comparative Example 1.
  • Example 1 The ion conductivity of each of the solid electrolyte materials of Examples 2 to 6 and Comparative Example 1 was measured as in Example 1. The measurement results are shown in Table 1.
  • Example 1 1.0LaOI•1.6LiI•0.4LiBH 4 1.6 0.4 I, BH 4 3.13 ⁇ 10 ⁇ 4
  • Example 2 1.0LaOI•1.2LiI•0.8LiBH 4 1.2 0.8 I, BH 4 1.07 ⁇ 10 ⁇ 3
  • Example 3 1.0LaOI•0.8LiI•1.2LiBH 4 0.8 1.2 I, BH 4 1.29 ⁇ 10 ⁇ 3
  • Example 4 1.0LaOI•0.4LiI•1.6LiBH 4 0.4 1.6 I, BH 4 1.55 ⁇ 10 ⁇ 3
  • Example 5 1.0LaOI•2.0LiBH 4 0 2.0 I, BH 4 1.39 ⁇ 10 ⁇ 3
  • Example 6 1.0LaOI•2.0LiI•1.0LiBH 4 2.0 1.0 I, BH 4 8.65 ⁇ 10 ⁇ 4 Comparative 1.0LaOI•2.0LiI 2.0 0 I, — 1.03 ⁇ 10 ⁇ 4
  • Example 2 1.0LaOI•1.6LiI
  • the solid electrolyte materials of Examples 1 to 6 had high lithium ion conductivity of greater than or equal to 3 ⁇ 10 ⁇ 4 S/cm at room temperature.
  • the battery of Example 1 was charged and discharged at room temperature.
  • the solid electrolyte material according to the present disclosure can improve lithium ion conductivity while preventing the generation of hydrogen sulfide.
  • the solid electrolyte material of the present disclosure is suitable for providing a battery that can be well charged and discharged.
  • the solid electrolyte material and method for manufacturing it of the present disclosure are used in, for example, a battery (e.g., an all-solid-state lithium ion secondary battery).
  • a battery e.g., an all-solid-state lithium ion secondary battery.

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